A New Family of Carbenerhodium(I) Complexes: Ligand Variation as The Key to Success

Abstract

Abstract:A synthetic methodology to obtain square-planar carbenerhodium (1)

Mono‐ and Dinuclear Rhodium and Iridium Complexes with Chiral Phospholanes as Ligands

“…Square-planar rhodium carbenes of the general compo- [26] the related phospholane derivatives 30 and 31 are catalytically inactive in olefin metathesis. However, they do react with ethene relatively fast (10 min in C 6 D 6 at room temperature) to give, apart from the ethene complexes 7 and 8 (and the dimer 2 in the case of Phephos as ligand), a mixture of two olefins 32 and 33 (see Scheme 8).…”

“…The starting materials [RhCl(C 8 H 14 ) 2 ] 2 , [32] [RhCl(PiPr 2 Ph) 2 ] 2 (10), [2] trans-[RhCl(ϭCPh 2 )(SbiPr 3 ) 2 ] (29), [26] and [IrCl(C 8 H 14 ) 2 ] 2 [33] were prepared as described in the literature. NMR spectra were recorded at room temperature (if not otherwise stated) on Bruker AC 200 and AMX 400 instruments and IR spectra on a PerkinϪElmer 1420 infrared spectrophotometer.…”

Tripropylarsane Complexes of Palladium(II) and Platinum(II) — Syntheses, Spectroscopy, and Structures

“…Although tertiary arsane (AsR 3 , R ϭ Me, Et, Pr) complexes of palladium have been known for quite sometime [10Ϫ12], studies on complexes of bulky arsanes (e.g. R 2 As(o-C 6 H 4 Me), AstBu 3 or AsiPr 3 ) with platinum group metals have been limited to the work of Shaw et al [13], Goel et al [14] and more recently to Werner et al [15]. In view of the above and in pursuance of our interest in design and development of organometallic precursors of group V elements, we have studied chemistry of AsPr 3 and AsiPr 3 complexes of palladium and platinum.…”

A Novel Route to Cationic Four-Coordinate Rhodium(I) Complexes with Rh=C Bonds

“…Recent attempts from our (PiPr 3 ) 2 ]X with L ϭ CO, C 2 H 4 and CϭCHR [5] turned out laboratory with the aim to prepare the cation trans-[Rh(ϭ to be not the method of choice for L ϭ CϭCϭCPh 2 . TreatCϭCϭCPh 2 ) 2 (PiPr 3 ) 2 ] ϩ unexpectedly led, via a novel CϪC ment of the mixture of [Rh(η 3 -C 3 H 5 )(PiPr 3 ) 2 ] and coupling, to the formation of two isomeric hexapentaene-[pyH]BF 4 with the propargylic alcohol HCϵCCPh 2 OH in rhodium(I) compounds of which the isomer having the acetone at room temperature led, within a short period of polyene coordinated in an unsymmetrical fashion is the time, to the formation of a deep red solution from which a thermodynamically more stable. [4] However, after we found red, moderately air-sensitive solid was obtained after rethat carbonyl-, ethene-and even vinylidenerhodium deriva-moval of the solvent.…”

“…TreatCϭCϭCPh 2 ) 2 (PiPr 3 ) 2 ] ϩ unexpectedly led, via a novel CϪC ment of the mixture of [Rh(η 3 -C 3 H 5 )(PiPr 3 ) 2 ] and coupling, to the formation of two isomeric hexapentaene-[pyH]BF 4 with the propargylic alcohol HCϵCCPh 2 OH in rhodium(I) compounds of which the isomer having the acetone at room temperature led, within a short period of polyene coordinated in an unsymmetrical fashion is the time, to the formation of a deep red solution from which a thermodynamically more stable. [4] However, after we found red, moderately air-sensitive solid was obtained after rethat carbonyl-, ethene-and even vinylidenerhodium deriva-moval of the solvent. According to the NMR spectra it contives such as trans-[Rh(py)(L)(PiPr 3 ) 2 ] ϩ and trans-sisted mainly of our target, the allenylidene complex trans-[Rh(NH 3 )(L)(PiPr 3 ) 2 ] ϩ (L ϭ CO, C 2 H 4 , CϭCHR) are ac-[Rh(py)(ϭCϭCϭCPh 2 )(PiPr 3 ) 2 ]BF 4 but also contained cessible and, with BF 4 Ϫ or PF 6 Ϫ as counterion, stable un-some impurities.…”